Coating composition



Patented July 21. 1937 a 2,088,052

\ UN TED "STATES PATENT OFFICE f COATING COMPOSITION g -George R. Ensminger, New Brunswick, N. 1., assignor to E. I. du Pont de Nemours & Com

. pany, Wihnington, Del., a. corporation of Dela.- w'are g No Drawing. Application June 19, 1936.

-' Serial No. 86,151 7 Claims. (01. 134-26) This invention relates to improved coating I Examp e compositions and more particularly to cellulose r cent by t derivative-vinyl resin compositions which po -mm oxide 11. 25 impri oved resistancegtochalking and bronz in Vinyl resin Solutiongfl 21. 40 5 s'serv ce. 7 l 1 '15.0

The films produced by theicommonly available fiifititietiiiiiiffiiiiififfffl 15.23 lacquers and enamels containing cellulo d v Ethyl alcohol (denatured) 14.20 tives such .ascellulose nitrate have a tendency T011101 6. 35 to assume when-exposed to atmospheric c Buty] acetate f 5. 10 t 10 tionsv a dull lifeless appearance. This is par- Dibutyl phthalate 5 00 10 ticularlythe case in'the lighter colors which High solvency petroleum hydrocarbomfl 3, 30 contain preponderant" quantities of white p'ig- Castor nil 3,20 ments such as zinc oxide, titanium oxide, ex-

tende'd'titanium oxide as Tltanox, etc. This y n l 100,00

15 defect which is commonly known in the protec- 1 r *This resin is. the product resulting from the joint s i as chalkmg lspfssentziauy sur polymerization of approximately 60% vinyl chloride and l D enomenon produced by 3 2' 1 1 p 1 40% vinyl acetate. The solution contains about 35% ficial disintegration of the protective film with n n a Solvent made from 5% s' acetate and the consequent freeing of the pigment particles. t0

20 Since the trend in recent years has been toward T enamel composition is prepared by first 20 the use of the lighter colored lacquer and enamels dispersing the p ent in a suitable p t of there is a demand for commercial products havthe Synthetic resin Solution. i dt by e ing improved resistance to this tendency of, addition. Of Solvents and diluents,in such pro- ,chalking. v I 1 portions as to permitworking the mass in a Another fault common to lacquers, particularly ball mill or another suitable device. This pig- 25 those containing considerable quantities of iron merited intermediate is then placed in an ordiblue pigments, is called bronzing. Itis often obnary paddle mixer together with the remaining served on dark blue automobiles which have been 1 ingredients in the proportions indicated, and the exposed to the weather for some time and conmixture is then thoroughly agitated until a i I sists of a. purplish or bronze discoloration. Somehomogeneous product is obtained. 30

55 claims.

times it is seen on maroon and red finishesel This invention has as an ob ect the provision Ewample 2 87mm Per cent by weight of an improved cellulose derivative coating composition which is characterized by the reduction Chinese blue pigment 7.00 35 or elimination of chalking and bronzing tenden- P 3 cies heretofore generally encountered when fi Vmyl 21-49 ishes prepared from cellulose derivative. compo- Cellulose mtiate (Vlscosity e se to the we or other E5231 'fiii of'zaa aa a;:::::::::::::: 1 4347. 40 erosive nd n a v Naphtha 5'93 0 Another object is. the provision of cellulose 'Dibutyl 'r; 5m) derivative protective anddecorative coating com- High Solvency petroleum 330 positions which will more'efiectively retain their vCastor oil 320 original lusterand which are more durable when Butyl acetate 310 subjected to atmospheric conditions. Amy] alcohol 5 These objects are accomplished by combining Buty] alcohol 1,11 cellulose derivatives with certain polymerization Citric acid .40 products of vinyl compounds and pigments which i normally tend to chalk or bronze. I i 100.00

The followmg examples: luflstr my The resin used in this example is the same as that of ierred embodiments; and it .will'beflunderstood e 5 p t s p g z r be m;

EI'SG in 8.0601 6.1109 W IOCGSS 011 l e 1 that Scope of the inventlon is not t c Opending application of Robert T. Hucks, Serial No. thereby except as set forth in the appended -9l,9o5,;filed Ju y .193

TM final enamel isprepared'by the method merit constituent described iorExample l which involves the addition of the "remaining ingredients of the com position to the pigmented intermediate in agitator mixer, in the proporti indicated and the charge is then thoroughly mixed until a homogeneous product is obtained.

While the white pigment used in Example 1 is leaded zinc oxide it is not intended to limit the invention to this particular pigment. Other white pigments such as regular zinc oxide, titanium oxide, extended titanium oxide pigments, Timonox, antimony oxide, zirconium oxide, barium, lead and zinc titanates, etc., may be used with the vehicles of the compositions either alone or in combination to produce white compositions or they may be present as such in pigment mixtures particularly those inwhich the white pigis present in predominant quantity.

It is realized that zinc, tin and iron pigments in straight vinyl vehicles react with the resin and cause the film to darken when baked at the required temperature (approximately 1hr. at 250 F.). However, in the case ofcellulose nitrate vinyl resin compositions of the present invention, the film may be force-dried for about 30 minutes at 140 F. and no reaction takes place. The improved enamels have shown no sign of darkening in service on automobile hoods after a period of two years nor have they shown any darkening on panels which have been exposed in Florida for extended periods. Zinc, tin and iron pigments, therefore, appear to be satisfactory from a stability angle for use in the cellulose nitrate vinyl resin-compositions of this invention.-

It has been found that the vehicles of the present invention are not only effective in eliminating bronzing tendencies of iron blue pigments in which this defect is most pronounced, such as Chinese, Prussian-and Milori blues as illustrated by Chinese blue in Example 2, but they are also effective in eliminating this defect in enamels prepared from other pigments, such as certain red, maroon and green pigments.

In maroon enamels containing appreciable proportions of some types of synthetic resins a considerable bronze has frequently developed immediately following conventional bufling and polishing practices, particularly as applied in the finishing of automobiles, sometimes to such an extent as to make the finish commercially unac ceptable and require complete refinishing of the affected areas. In the maroon enamels of the present invention, however, this defect is eliminated, thus afifording a finish that is of outstanding merit in preventing the formation of this type of bronze.

It is also necessary in order to obtain maximum chalk resistance with acceptable working properties that the cellulose 'nitrate vinyl resin plasticizer ratios be kept within certain limits. These ratios should be such that for each 10 parts by weight of cellulose nitrate, the amount of resin is not more than 10 parts, but not less than about 5 parts. If the ratio of resin to cellulose nitrate is substantially increased, the commercial utilization of these compositions is reduced because the sanding, rubbing and polishing operations customarily followed in the finish ing industry cannot be satisfactorily practiced.

The amount of plasticizer is about 2 parts when,

the maximum quantity of resin is used and is about 5 parts when the minimum amount of resin is used. If the resin ratio is reduced below the limit given, the degree of chalk resistance obtained is not of commercial significance. In general the amount of resin required for correcting bronzing tendencies is less than the amount required to provide chalk resistance in compositions containing chalking type pigments."

The types and proportions of solvents and diluents shown in the above examples may be varied over a considerable range and the substitution of an equivalent material or a change in proportions to suit conditions of application or other special requirements is considered within the ordinary practice of one skilled in the art.

The resin constituent of the new compositions is preferably a product resulting from the interpolymerization of vinyl chloride and vinyl acetate compounds. The vinyl derivatives, vinyl chloride and vinyl acetate, are prepared according to methods well known in the art. The process of polymerizing vinyl derivatives in mutual contact is disclosed in U. S. Patent 1,867,014. The resulting polymers are different from the mixtures of the esters polymerized separately, in that the product is tough and strong and is much better adapted to the purposes of. the enamel industry with respect to adhesiveness and stability.

The coatirg compositions described herein may be utilized for finishing'surfaces which are to be exposed to the destructive forces of the atmosphere. They find particular application as a protective coating for surfaces exposed to severe weather conditions, such as the finish of automobiles.

, The coating compositions of the present invention are characterized by extraordinary life and durability, thus afiording obvious economy for the consumer. Chalking and bronzing defects are greatly reduced or entirely eliminated, and as a result the true color and original gloss of the finish are retained over a greater period.

Another advantage resides in the-fact that ordinary films require frequent cleaning and polishing to retain a satisfactory appearance. However, with a. film produced. from the compositions of the present invention this labor is reducgi to a'minimum, and a finish is secured which resists flaking, cracking, and peeling to a very high degree.

It is apparent that many widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof; and, therefore, it is not intended to be limited. except as indicated in the appended claims.

I claim:

1. Coating composition a dry film of which remains free from chalking and bronzing under prolonged exposure to atmospheric conditions comprising a cellulose derivative, a resin resulting from the interpolymerization of a vinyl halide and a vinyl ester of the lower fatty acid series, a pigment which normally chalks or bronzes in a cellulose nitrate film, a plasticizer, and a volatile solvent for the resin and the cellulose derivative.

2. A coating composition a dry film of which remains free from chalking and bronzing under prolonged exposure to atmospheric conditions comprising a cellulose derivative, a resin resulting from the interpolymerization of vinyl chloride and vinyl acetate, a pigment which normally chalks or bronzes in a cellulose nitrate film, a

plasticiger, and a volatile solvent for the resin and ly the following formula:

v Per cent by weight Chinese blue pigment 7.00 Zinc oxide .80 Vinyl resin solution 21.40 Cellulose nitrate (viscosity sec.) 15.00 Ethyl acetate 17.93 Ethyl alcohol (denatured) 14.47 Naphtha 5.93 Dibutyl phthalate 5.00 High solvency petroleum hydrocarbn 3.30 Castor oil 3.20 Butyl acetate 3.10 Amyl alcohol 1.36 Butyl alcohol 1.11 Citric acid .40

of cellulose derivative, and said plasticizer being present in amount between .5 and .2 parts for each part of cellulose derivative.

3. A coating composition havingapproximate- 4. A coating composition having" approximately the following formula:

5. Product of claim 1 in which the cellulose derivative is cellulose nitrate and the pigment is leaded zinc oxide. 1

6. Product of claim 1 in which the cellulose derivative is cellulose nitrate and the resin is the interpolymer of approximately 60%vinyl chloride and 40% vinyl acetate.

Per cent by weight Leaded zinc oxide 11.25 Vinyl resin solution 21.40 Cellulose nitrate (viscosity sec.) 15.00 Ethyl acetate 15.20 Ethyl alcohol (denaturedLi. 14.20 Toluo1 6.35 Butyl acetate 5.10 Dibutyl. phthalate; 5.00 High solvency petroleum hydrocarbon 3.30 Castor oil 3.20

7. Product of claim 1 in which the pigment is an iron blue pigment.

GEORGE R. ENSMINGER. 

